JP2020510123A - Storage stable rigid foam formulation - Google Patents

Abstract

The shelf life of a B-side composition comprising a polyol, a surfactant, a blowing agent, an organometallic or metal salt catalyst, and 1 to 10 weight percent water, where the metal of the catalyst comprises Zn or Bi, is It is improved by addition. [Selection diagram] Fig. 1

Description

    The present disclosure relates to a polyol premix composition. More specifically, the present disclosure relates to polyol premix compositions useful for preparing rigid foams.

    The use of halogenated olefin blowing agents in the production of polyurethane and / or polyisocyanurate rigid foams, especially trans-1,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene When such species are pre-mixed with the polyol, catalyst, surfactant, and flame retardant (B side of the formulation) and stored at ambient conditions, a gradual decomposition reaction occurs in the formulation and foaming It was observed that the body quality was reduced and the reactivity and properties of the formulation changed. These adverse effects are exacerbated at higher temperatures and / or in the presence of water. It is desirable to have a B-side composition with improved shelf life.

    The B-side composition of the present disclosure is such a B-side composition useful for preparing rigid foams, wherein the composition comprises a polyol, a surfactant, a blowing agent, a thiol compound, a weight of the composition. 1 to 10% by weight of water, and the metal of the catalyst comprises an organometallic or metal salt catalyst comprising Zn or Bi.

    Surprisingly, the B-side composition of the present disclosure has an improved shelf life.

FIG. 1 is a graphical representation of foam height versus time accelerated aging results for Example 1. FIG. 2 is a graphical representation of foam height versus time accelerated aging results for Example 2. FIG. 3 is a graphical representation of foam height versus time accelerated aging results for Example 3. FIG. 4 is a graphical representation of foam height versus time accelerated aging results for Comparative Example 4. FIG. 5 is a graphical representation of foam height versus time accelerated aging results for Example 5. FIG. 6 is a graphical representation of foam height versus time accelerated aging results for Comparative Example 6.

    The present disclosure provides a high water content polyol premix composition comprising a combination of a blowing agent, one or more polyols, one or more surfactants, thiols, 1-10 weight percent water, and an organometallic or metal salt catalyst. I will provide a. Further, the present disclosure includes a process for preparing such a composition.

    The present disclosure also provides a method of preparing a polyurethane or polyisocyanurate foam, comprising reacting an organic polyisocyanate with a polyol premix composition.

    As used herein, the terms "a," "an," "the," "at least one," and "one or more" are used interchangeably. The terms "comprise" and "include", and variations thereof, do not have a limiting meaning where these terms appear in the description and claims. Thus, for example, a material “a (one)” can be interpreted to mean “one or more” materials, and a composition “include” or “comprise” a material means that the composition This can be taken to mean including things in addition to materials.

    A "complex" is defined as a bond formed by the bonding of one or more electronically poor molecules or atoms, each of which can independently exist, with one or more electronically rich molecules or atoms, which can independently exist. Position compound.

    Unless otherwise stated, unless otherwise implicit in context or customary in the art, all parts and percentages are by weight and all test methods are current at the time of filing of the disclosure. Things. The abbreviation "% by weight" represents percent by weight.

    "Storing life of at least 4 months" refers to (a) the measured reactivity of the formulation (any one of cream, gel, and tack-free time) or (b) the resulting foam product. At least one of the free rise densities varies by more than 25% in the handmix cup foam sample, as determined by the accelerated aging test procedure described below, as compared to the corresponding time of the initial control sample. It means the time needed. This test is expected to mimic the changes that would be observed during storage for more than 4 months at ambient conditions.

    As used herein, the terms "polyol premix composition" and "B-side composition" are used interchangeably.

    As used herein, the term "HFO" refers to hydrofluoroolefin. As used herein, the term "HCFO" refers to hydrochlorofluoroolefin.

    As used in connection with a thiol compound, "stoichiometric excess" means that the number of moles of thiol moiety present exceeds the number of moles of active metal species in the metal catalyst. For example, if the catalyst is one mole of a divalent Zn compound, more than one mole of a monofunctional thiol compound is used.

Water is used in the polyol premix composition. When producing a foam using a premix, an amount sufficient to produce a rigid foam having a free rise density of 0.5 to 20.0 lbs / ft ³ , preferably 1.2 to 2.5 lbs / ft. Of water is used. In various embodiments, the polyol premix comprises 1-10% water, 2-5% water, or 3-5% water by weight, based on the weight of the polyol premix composition. The amount of water includes water from any source, such as a blowing agent or other component of the composition of the present disclosure.

    Thiols are used in polyol premix compositions. “Thiol” is an organic compound having at least one —SH (mercapto) group. In one embodiment, the thiol compound has a total of 3 to 25 carbon atoms, preferably 5 to 17 carbon atoms. The thiol is used in stoichiometric excess with respect to the metal catalyst, as that term is defined above. In various embodiments, the polyol premix comprises 0.0001-10 wt% thiol, 0.01-5.0 wt% thiol, or 0.1-1 wt%, based on the weight of the polyol premix composition. It contains 0.5% by weight of thiol.

    Thiols are used in conjunction with bismuth and / or zinc catalysts. It is not known exactly what kinetics occur for the catalyst / thiol mixture to produce a hydrolytically stable catalyst for storage in a polyol premix composition. While not wishing to be bound by any particular theory at this point, nonetheless, the thiol compound stabilizes some or all of the ligands on the bismuth / zinc catalyst and allows the water molecule to attach to the catalyst. Preventing access is believed to inhibit hydrolysis of the metal catalyst.

In one embodiment, the thiol is a solid dispersed in a liquid or liquid diluent at ambient temperature and pressure. The thiol may be a monofunctional species in which a single thiol moiety is present or a polyfunctional species in which multiple thiol moieties and / or other isocyanate-reactive moieties are present. Examples of suitable thiols include those substituted aromatically (eg, benzylthiol), mercaptoacetate, mercaptopropionate, poly (ethylene glycol) methyl ether thiol, dithiol, bis-PEG-thiol, trithiol, thioglycerol. _{, HSCH 2 CH (OH) CH} 2 OH, thiol -PEG- alcohol, cysteine, as well as include saturated or unsaturated alkyl thiol derivatives thereof and mixtures thereof, without limitation.

    The polyurethane catalyst of the present disclosure is advantageously mixed with at least an equimolar amount of thiol in a suitable diluent, preferably with a stoichiometric excess of thiol. As long as this proportionality requirement is satisfied, the thiol / catalyst ratio can otherwise vary significantly. However, the molar ratio of the thiol moiety to the active metal species of the metal catalyst is 1: 1 to 1000: 1, preferably 1.1: 1 to 10: 1, preferably 2: 1 to 6: 1, especially 2: Preferably it is in the range of 1-4: 1. The diluent may comprise anywhere from 0 to 99%, preferably 40 to 80% by weight of the catalyst / thiol / diluent mixture, based on the weight of the mixture. Examples of diluents include polyols, alcohols, ketones, ethers, esters, cyclic and acyclic alkanes, alkenes, alkynes, hydrocarbons, other polar and non-polar solvents, and the like, and combinations thereof.

The blowing agent can be selected from a wide variety of blowing agents. The water used in the polyol premix functions as a part of the blowing agent, so that a mixture of blowing agents can be used. In certain embodiments, the blowing agent is one or more hydrohaloolefins, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, Including ketones, organic acids, water, other gas generating materials, or combinations thereof. Examples of blowing agents include halogenated olefins such as 1233zd, 1234ze, 1,1,1,4,4,4-hexafluoro-2-butene (1334mzz, and 1,2-dichloroethylene), hydrocarbons such as cyclo Pentane, n-pentane, isopentane, and isobutane), hydrofluorocarbons such as HFC-134a, HFC-245fa, HFC-365mfc, hydrochlorofluorocarbons such as HCFC-141b, fluorocarbons, chlorocarbons, chlorofluorocarbons such as CFC-11) , Halogenated ethers, ethers, esters, eg, methyl formate), aldehydes, ketones, eg, acetone), CO ₂ generating materials, eg, water and formic acid), and combinations thereof.

    In one embodiment, the blowing agent is preferably 1234ze (E), 1233zd (E), and an isomer blend thereof, and / or 1336mzzm (Z), and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluoro Including hydrohaloolefins including at least one or a combination of chlorocarbons, halogenated hydrocarbons, ethers, fluorinated ethers, esters, alcohols, aldehydes, ketones, organic acids, gas generating materials, water, or combinations thereof. .

    The hydrohaloolefin preferably comprises at least one haloalkene, such as a fluoroalkene or chlorofluoroalkene containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins include, but are not limited to, trifluoropropene, tetrafluoropropene such as (1234), pentafluoropropene such as (1225), chlorotrifluoropropene such as (1233), chlorodifluoropropene, and chlorotriene. Fluoropropene, chlorotetrafluoropropene, hexafluorobutene (1336), and combinations thereof. More preferred as compounds are tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds having at most one unsaturated terminal carbon having an F or Cl substituent. 1,3,3,3-tetrafluoropropene (1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (1225ye), 1,1,1- Trifluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluoropropene (1225zc) and 1,1,2,3,3-pentafluoropropene (1225yc ), (Z) -1,1,1,2,3-pentafluoropropene (1225yez), 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,1,4,4 Includes 4-hexafluorobut-2-ene (1336mzzm) or a combination thereof, as well as each and every stereoisomer of each.

    Preferred hydrohaloolefins have a global warming potential (GWP) of 150 or less, more preferably 100 or less, even more preferably 75 or less. As used herein, "GWP" is used to refer to "The Scientific Assessment of Ozone Depletion, 2002, a report of the Worldwide Medical Association Medical Association's Association of Gazettes", which is incorporated herein by reference. As measured for carbon dioxide GWP, over a period of 100 years. Preferred hydrohaloolefins also have an ozone depletion potential (ODP) of preferably 0.05 or less, more preferably 0.02 or less, and even more preferably about zero. As used herein, "ODP" refers to "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Medical Association's Medical Association's Association of Gazettes, Inc., which is incorporated herein by reference. It is as it is.

Further examples of blowing agents include, but are not limited to, CO ₂ and / or CO, hydrocarbon-forming organic acids, ethers, halogenated ethers, esters, alcohols, aldehydes, ketones, pentafluorobutane, pentafluoropropane, Hexafluoropropane, heptafluoropropane, trans-1,2-dichloroethylene, methylal, methyl formate, 1-chloro-1,2,2,2-tetrafluoroethane (124), 1,1-dichloro-1-fluoroethane ( 141b), 1,1,1,2-tetrafluoroethane (134a), 1,1,2,2-tetrafluoroethane (134), 1-chloro-1,1-difluoroethane (142b), 1,1,1 , 3,3-pentafluorobutane (365mfc), 1,1,1,2,3,3,3-hepta Fluoropropane (227ea), trichlorofluoromethane (11), dichlorodifluoromethane (12), dichlorofluoromethane (22), 1,1,1,3,3,3-hexafluoropropane (236fa), 1,1, 1,2,3,3-hexafluoropropane (236ea), 1,1,1,2,3,3,3-heptafluoropropane (227ea), difluoromethane (32), 1,1-difluoroethane (152a) , 1,1,1,3,3-pentafluoropropane (245fa), butane, isobutane, normal pentane, isopentane, cyclopentane, or a combination thereof. In certain embodiments, the blowing agent comprises water and / or a combination of normal pentane, isopentane, or cyclopentane, which may comprise one of the hydrohaloolefin blowing agents discussed herein or a combination thereof. It can be provided with a combination. The blowing agent is preferably present in an amount of 1% to 30%, preferably 3% to 25%, more preferably 5% to 25% by weight of the polyol premix, based on the weight of the polyol premix composition. Present in the composition. These amounts do not include the water present in the premix composition. For example, a polyol premix composition may include 1% to 30% by weight (non-aqueous) blowing agent and 1 to 10% by weight water.

    The polyol, including a mixture of polyols, can be any polyol or mixture of polyols that reacts with isocyanates in a manner known in preparing polyurethane or polyisocyanurate foams. Useful polyols include sucrose containing polyols, phenol, phenol formaldehyde containing polyols, glucose containing polyols, sorbitol containing polyols, methyl glucoside containing polyols, aromatic polyester polyols, glycerol, ethylene glycol, diethylene glycol, propylene glycol, polyether polyols and vinyl One or more of a graft copolymer with a polymer, a copolymer of a polyether polyol and a polyurea, and (a) glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, Selected from palm oil and castor oil, wherein (b) is ethylene oxide, propylene oxide, ethylene oxide and Mixture of pyrene, and combinations thereof, including one or more of (b) engaged one or more condensed out in (a). The polyol component is usually present in an amount of 60% to 95%, preferably 65% to 95%, more preferably 70% to 90% by weight of the polyol premix composition, based on the weight of the polyol premix composition. Present in the mix composition.

    The polyol premix composition also contains a surfactant. Surfactants are preferably used to form the foam from the mixture and to control the foam size of the foam such that a foam of the desired cellular structure is obtained. Preferably, the foam has the most desirable physical properties, such as compressive strength and thermal conductivity, so that a foam having small bubbles or cells of uniform size therein is desirable. It is also advantageous to have a foam with stable cells that does not collapse before or during foaming.

    Surfactants for use in preparing polyurethane or polyisocyanurate foams are well known to those skilled in the art and many are commercially available. Such materials have been found to be applicable to a wide range of formulations that allow for uniform cell formation and maximum gas entrapment to achieve very low density foam structures. Surfactants can include silicone or non-silicone surfactants, or combinations thereof. Preferred silicone surfactants include polysiloxane polyoxyalkylene block copolymers. Some exemplary silicone surfactants useful in the present disclosure include Momentive's L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L-980. 6988; Dow Corning's DC-193, DC-197, DC-5582, and DC-5598; and B-8404, B-8407, B-8409, and B- from Evonik Industries AG, Essen, Germany. 8462. Others are disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, 2,846,458, and 4,147,847. The surfactant may comprise from 0.5% to 6.0%, preferably from 1.0% to 4.0%, more preferably from 1.5% to 1.5% by weight, based on the weight of the polyol premix composition. It is present in the polyol premix composition in an amount of 3.0% by weight.

    Examples of non-silicone surfactants include oxyethylated alkyl phenols, oxyethylated fatty alcohols, paraffin oil, castor oil esters, ricinoleic acid esters, turkey oil, peanut oil, paraffin, silicone surfactants, and fatty alcohols. A preferred non-silicone surfactant is Vorasurf 504, commercially available from The Dow Chemical Company.

    Catalysts include metal-containing catalysts, referred to herein as "metal catalysts", and are preferably organometallic or metal salt catalysts. In one embodiment of the present disclosure, the catalyst is preferably a zinc-based or bismuth-based catalyst, or a combination of a zinc-based catalyst and a bismuth-based catalyst. In one embodiment of the present disclosure, the catalyst is a metal-containing non-amine catalyst such as an organometallic compound or metal salt. In one embodiment of the present disclosure, the B-side composition does not include an added amine catalyst. In one embodiment of the present disclosure, the metal catalyst may be combined with any potassium-based cocatalyst, such as potassium acetate or potassium octoate. In one embodiment of the present disclosure, the catalyst may include any amine co-catalyst. Examples of suitable amine cocatalysts include aliphatic or aromatic, cyclic or acyclic tertiary amines. Preferred optional amine cocatalysts include Polycat 8 (Air Products), Polycat 12 (Air Products), Polycat 203 (Air Products), Polycat 204 (Air Products), and Polycat 210 (Air Products). , Polycat 218 (Air Products), Dabco 2040 (Air Products), Dabco T (Air Products), RC-102 (Rhein Chemie), Jeffcat DMDEE (Huntsman), Huntsman, Jfat ), Jef cat DMP (Huntsman), N. N-dimethyl-p-toluene, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, dimorpholinodimethylether, and triethanolamine.

    Examples of metal salts or organometallic catalyst compounds include, but are not limited to, bismuth and / or zinc organic salts, Lewis acid halides, and the like. Non-exclusive examples of such metal salts or organometallic catalysts include zinc oxide, zinc nitrate, zinc acetate, zinc neodecanoate, zinc octanoate, zinc hexanoate, zinc acetylacetonate, zinc ethoxide, zinc propoxide, Zinc butoxide, zinc isopropoxide, zinc 2-ethylhexanoate, zinc carboxylate, bismuth nitrate, bismuth neodecanoate, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth carboxylate, BiCAT Z, BiCAT 8 , BiCAT 8106, BiCAT 8108, BiCAT 8118, BiCAT 8210, BiCAT 8840, BiCAT 8842, K-Kat XK-651, K-Kat XK-661, K-Kat XK-635, K-Kat XK-604, K-Kat XK 614, K-Kat XK-617, K-Kat XK-618, K-Kat XC-B221, Reaxis C739W50, Reaxis C739E50, Reaxis C716, Reaxis C717, Reaxis C726, Reaxis C708, ReaxisCix6C6 , TROYMAX Zinc 8, TROYMAX Zinc 10, TROYMAX Zinc 12, TROYMAX Zinc 16, TROYMAX Bismuth 24, and combinations thereof, but are not limited thereto. In certain preferred embodiments, the catalyst comprises 0.001% to 5.0%, 0.01% to 3.0%, preferably 0.3% by weight, based on the weight of the polyol premix composition. % To 2.5% by weight, more preferably 0.35% to 2.0% by weight, in the polyol premix composition. These are conventional amounts, but the amounts of the aforementioned catalysts can vary widely, and appropriate amounts can be readily determined by one skilled in the art.

    The preparation of polyurethane or polyisocyanurate foams using the compositions described herein, which can follow any of the methods well known in the art, can be used. Generally, polyurethane or polyisocyanurate foams are prepared by combining isocyanates, polyol premix compositions, and other materials such as optional flame retardants, colorants, or other additives. These foams can be rigid or semi-rigid and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells.

    In many applications, it will be convenient to provide the components for the polyurethane or polyisocyanurate foam in a pre-blended formulation. Most typically, the foam formulation is pre-blended into two components. Isocyanates and optional other isocyanate-compatible ingredients, including, but not limited to, blowing agents and certain silicone surfactants, include a first component, commonly referred to as an "A" component or an A-side composition. . The polyol blend composition comprising the surfactant, catalyst, blowing agent, and any other components includes a second component, commonly referred to as the "B" component or B-side composition. For any given application, the "B" component may not contain all of the components described above; for example, some formulations may be flame retardant if they do not have the foaming properties required for flame retardancy. Exclude Thus, polyurethane or polyisocyanurate foams can be prepared by hand mixing the A-side and B-side components for small amounts of preparation, and also preferably using blocks, slabs, laminates, cast-in panels and other Are easily prepared together by mechanical mixing techniques to form items, spray-applied foams, froths and the like. Optionally, other components such as flame retardants, colorants, auxiliary blowing agents, water, and even other polyols can be added as a stream to the mixing head or reaction site. However, most conveniently, as noted above, they are all incorporated into one B component.

    Foamable compositions suitable for forming polyurethane or polyisocyanurate foams can be formed by reacting an organic polyisocyanate with the polyol premix composition described above. Any organic polyisocyanate can be used for polyurethane or polyisocyanurate foam synthesis, including aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include the aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates well known in the field of polyurethane chemistry. Preferred as a class are aromatic polyisocyanates.

An exemplary organic polyisocyanate corresponds to the formula: R (NCO) _z , where R is a polyvalent organic radical that is either aliphatic, aralkyl, aromatic, or a mixture thereof; Is an integer corresponding to the valence of R, and is at least 2. Representative examples of organic polyisocyanates contemplated herein include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, crude Aromatic diisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate, aromatic triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate and 2,4,6-toluene isocyanate; Aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5-'tetraisocyanate; arylalkyl polyisocyanates such as xylylene diisocyanate; hexamethylene- , 6-diisocyanate, aliphatic polyisocyanates such as lysine diisocyanate methyl ester, and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, and 4,4′-biphenylene Diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate. , Typical aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorylene diisocyanate, 4,4'-methylene bis (cyclohexyl Alkylene diisocyanates such as m.- and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluene diisocyanate, and dianisidine diisocyanate. , Bithylene isocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanatophenyl) methene, bis (2-methyl-4-isocyanatophenyl) methane and the like. Preferred polyisocyanates are polymethylene polyphenyl isocyanates, especially mixtures containing 30 to 85 weight percent methylene bis (phenyl isocyanate), with the balance of the mixture comprising polymethylene polyphenyl polyisocyanates of greater than 2 functionality. These polyisocyanates are prepared by conventional methods known in the art. In one embodiment of the present disclosure, the polyisocyanates and polyols are used in amounts that provide an NCO / OH stoichiometry in the range of 0.9 to 7.0. In one embodiment of the present disclosure, the NCO / OH equivalent ratio is preferably 1.0 or more and 3.0 or less, and an ideal range is 1.1 to 2.5. Particularly suitable organic polyisocyanates include polymethylene polyphenyl isocyanate, methylene bis (phenyl isocyanate), toluene diisocyanate, and combinations thereof.

    In preparing the polyisocyanurate foam, a trimerization catalyst is used to convert the blend with excess A component to a polyisocyanurate-polyurethane foam. The trimerization catalysts used include, but are not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylate, and alkali metal carboxylate salts, and mixtures of various types of catalysts. It can be any catalyst known to those skilled in the art. Preferred species within the class are potassium acetate, potassium octoate, and sodium N- (2-hydroxy-5-nonylphenol) methyl-N-methylglycinate.

    Conventional flame retardants can also be incorporated, preferably in an amount up to 30 weight percent on the combined A and B sides. Examples of optional flame retardants include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate. ), Tri (2-chloroisopropyl) phosphate, tricresyl phosphate, tri (2,2-dichloroisopropyl) phosphate, N, N-bis (2-hydroxyethyl) aminomethylphosphonic acid, dimethyl methylphosphonate, triphosphate (2,3-dibromopropyl), tri (1,3-dichloropropyl) phosphate, and tetra-kis- (2-chloroethyl) ethylene diphosphate, triethyl phosphate, diammonium phosphate, various halogenated aromatics Group compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, melamine and the like.

    In addition to the components described above, other components such as dyes, fillers, pigments, and the like can be included in the preparation of the foam. Dispersants and cell stabilizers can be incorporated into the blend. Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black, and silica. Fillers, when used, are typically present in a weight range of 5 to 100 parts per 100 parts of polyol. Pigments that can be used herein include titanium dioxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue siena, molybdenum orange, and organics such as para red, benzidine yellow, toluidine red, toner, and phthalocyanine. It can be any conventional pigment, such as a pigment.

    The resulting polyurethane or polyisocyanurate foam has a density (in-situ density) of 0.5 pounds per cubic foot to 60 pounds per cubic foot, preferably 1.0 to 20.0 pounds per cubic foot, most Preferably it can vary from 1.5 to 6.0 pounds per cubic foot. The resulting density may be in the A and / or B components or the blowing agent or the amount of auxiliary blowing agent, such as water or other co-blowing agent added at the time the foam is prepared. It is a function of the amount of blowing agent mixture. These foams can be rigid or semi-rigid foams and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells. These foams are used in a variety of well-known applications, including but not limited to thermal insulation, cushions, flotation, packaging, adhesives, cavity filling, craft decorations, and shock absorption.

Specific Embodiments Accelerated Aging Test Procedure A sufficient amount of the B-side formulation (adding 10% to account for loss when opening the container) containing a blowing agent is loaded into a steel pressure vessel with ball bearings. Enter.

    Record the weight of the material in the pressure vessel.

    Place the container on a roller system and mix the contents for 30-60 minutes.

    Decant the required amount of B-side formulation to make a cup foam (45 g B-side and 50 g PAPI 27 for reactivity measurement, 71 g B-side and 79 g PAPI 27 for FOAMAT analysis) and cream Note the time, gel time, tack free time, foam height versus time, and free rise density. These data indicate the initial reactivity of these systems.

    Place the pressure vessel in the secondary vessel and place in a 50 ° C. (122 ° F.) oven. Monitor the pressure in the container to ensure that the system does not over-press and prevent the blowing agent from leaking.

    Each week, remove the pressure vessel from the oven, mix on a roller system for about 4 hours, and cool to room temperature.

    Once at room temperature, check the initial weight of the container. Decant the required amount of B-side formulation and make cup foam as described above, again paying attention to cream time, gel time, tack free time, foam height versus time, and free rise density . If the flow on the B side is slow, purge the vessel with nitrogen. A newly generated control analysis is included to account for changes in ambient conditions.

    Measure the remaining amount of material in the container.

    Return the container to the oven and repeat the process weekly for two weeks.

    This procedure is used in the following examples and comparative experiments using the materials described therein.

Materials List Polyol 1 is a sucrose / glycerin initiated polyether polyol having a nominal hydroxyl functionality of about 4 and an OH # = 360 mg KOH / g, available from The Dow Chemical Company, and polyol 2 is also a The Dow Chemical A glycerin-initiated polyether polyol having a nominal hydroxyl functionality of about 3 and an OH # = 235 mg KOH / g, available from Company. PAPI ™ 27 brand polymer MDI is a polymethylene polyphenyl isocyanate containing MDI and is available from The Dow Chemical Company.

Example 1 A rigid foam formulation comprising HCFO, an organometallic or metal salt catalyst, and a thiol stabilizer. Note: The catalyst loading is adjusted to match the gel time of both formulations, pre-blend the organometallic or metal salt catalyst, thiol, and glycol before adding to the formulations.

Example 2: Rigid foam formulation with HCFO, organometallic or metal salt catalyst, and thiol stabilizer and the same metal content as Comparative Experiment 4. The organometallic or metal salt catalyst, thiol, and glycol are pre-blended before adding to the formulation.

Example 3: A rigid foam formulation containing HCFO, an organometallic or metal salt catalyst, and a different thiol stabilizer (cetyl thiol), and having the same metal content as Comparative Experiment 4. Note: The catalyst loading and formulation was adjusted to correspond to a gel time of about 120 seconds, prior to adding the organometallic or metal salt catalyst, thiol, and a portion of polyol 2 before adding to the formulation. Blend.

Comparative Experiment 4 (not an embodiment of the present disclosure): Rigid foam formulation containing only HCFO and organometallic or metal salt catalyst.

    By comparing the results of Examples 1 to 3 with the results of Comparative Experiment 4, it was found that the elimination of thiol significantly changed the gel time and tack free time of the system (> 25%), This suggests that the catalytic activity in the product decreases with time.

Example 5: A rigid foam formulation comprising HCFO, a bismuth-based organometallic or metal salt catalyst, and a thiol stabilizer. The catalyst is a bismuth catalyst available as BiCAT 8842 (Shepherd Chemical Company). Note: The catalyst and thiol are pre-blended into a portion of the polyol mixture before being added to the formulation.

Comparative Experiment 6 (not an embodiment of the present invention): a rigid foam formulation containing only HCFO and a bismuth-based organometallic or metal salt catalyst.

    Comparing the results of Example 5 with the results of Comparative Experiment 6, it can be seen that the elimination of the thiol significantly changes the gel time and tack free time of the system, which indicates that the catalyst activity in the formulation is time dependent. It suggests that it has declined.

    Thus, the B-side composition of the present disclosure provides an unexpectedly improved shelf life according to the shelf life definition provided herein. More specifically, the overall change in physical properties is much smaller in the examples than in the comparative experiments, which indicates that those systems are more stable and have a longer shelf life, such as at least a four month shelf life. It has a shelf life.

Claims (10)

    A B-side composition useful for preparing a rigid foam, comprising a polyol, a surfactant, a foaming agent, a thiol compound, 1 to 10 weight percent water, based on the weight of the composition, and an organometallic or metal. A B-side composition comprising a salt catalyst, wherein the metal of the catalyst comprises Zn or Bi.     2. The composition of claim 1, wherein said composition has a shelf life of at least 4 months.     The composition according to claim 1, wherein the amount of water is 2 to 5% by weight.     The composition according to any one of claims 1 to 3, wherein the amount of the water is 3 to 5% by weight. The thiol is an aromatic-substituted alkyl thiol (for example, benzyl thiol), mercapto acetate, mercapto propionate, poly (ethylene glycol) methyl ether thiol, dithiol, bis-PEG-thiol, trithiol, thioglycerol, HSCH _{2 CH} (OH) CH 2 OH, comprising a thiol -PEG- alcohols, cysteine and derivatives and mixtures, saturated or unsaturated alkyl thiol, composition according to any one of claims 1-4.     The foaming agent comprises at least one of trans-1,3,3,3-tetrafluoropropene (1234ze) and 1-chloro-3,3,3-trifluoropropene (1233zd). The composition according to any one of claims 1 to 5.     The composition according to any one of claims 1 to 6, wherein a stoichiometric excess of the thiol is used.     The composition comprises 60-95% by weight of polyol, 0.5-6.0% by weight of surfactant, 1-30% by weight without considering water, based on 100% by weight of the composition. 8. A composition as claimed in any one of the preceding claims, comprising a blowing agent, 0.0001 to 10% by weight of a thiol compound, 0.001% to 5.0% by weight of a catalyst, and 1 to 10% by weight of water. A composition as described.     A rigid foam prepared from a mixture of (a) the A-side composition containing isocyanate and (b) the composition according to any one of claims 1 to 8. Polyols, surfactants, blowing agents, thiol compounds, organometallic or metal salt catalysts, and 1 to 10 weight percent water, based on the weight of the composition, under conditions such that the B-side composition is prepared. Including mixing,
The metal of the catalyst comprises Zn or Bi;
process.